Catalytic conversion of hydrocarbons



June 19, 1945. w. KIERS TED, JR 2,378,734

v CATALYTIC CONVERSION OF HYDROCARBONS I Filed Sept. 1 0, 1945.

REACTION TOW E R A ISOMATE;

EXCHANGER BYPASS e l 24 Al I HEAT5R A A 4, .1 I STRIPPED ISOMA'IE HCI . 1 -COMPLEX SCRUBB'ER ENRICHED COMPLEX ',STRIPPER HEAT EXCHANGER 2x3L V WYNKOOP' KIERSILED l VENTOR J7! Patented June 19, 1945 UNITED STATES PATE NT. OFFICE- chloride is eilective as a catalyst.

CATALYTIC CONVERSION OF HYDROCARBON S Wynkoop Kiersted, In, New York. N. Y... assigno r to, The Texas Company, New York, "N. Y.,a 00,1".

poration of Delaware l Application September 10, 1943, Serial 140.501.1515

'iol ims; ((1260-6835) This invention relates to a continuous process for efiecting catalytic conversions such as the isomerization of hydrocarbons.

The invention contemplates eiiecting catalytic conversion of hydrocarbons with a metallic halide catalyst such as aluminum chloride under condia tions such that metallic halide-hydrocarbon complex is formed usually in relatively small amount.

The invention involves carrying out the conversion in a-packed tower wherein a stream of feed hydrocarbons advantageously in vapor phase is caused to rise through the tower countercurrently to and in direct contact with aliduid comprising aluminum chloride dissolved in hydrocarbons and some-complex. The reaction tower is maintained under conditions reaction. a

A stream of hydrocarbons containing'hydro carbon products of reaction is continuously dis- :suitable for effecting the desired liquid containing dissolved metallic halide catalyst. The reaction tower :is maintained at a temperature of about 206 t 220 F. or at a temperature within the range 160 to 240 Contact between the flowin catalyst andihydrocarbon is efiected in the presence ota suitable promoter such as hydrogen chloride so that isomer ization of normal butane to isobutane occurs as the principalreaction. I

Asmall amount of the feedhydrocarbonsenters into reaction with the metallicihalide; forming liquid complex compounds which descend through the packing materialcountercurrently to the rise ing butane vapors charged fromithe upper portion of the reaction tower while a stream comprising complex liquid is discharged from the bottom or lower portion of the tower.

A feature of the invention involves cheating n A stream of isobutane and unrcacted normal butane is continuously drawn ofi iromthe. top of the tower while complex liquid and any heavier hydrocarbonsthat. may :be formed inthe reaction I discharged from the bottom. of

are continuously the tower.

Temperature conditionsand promoter concen tration may be adju ted so that substantially no countercurrent contact between a stream .of feed hydrocarbons and the catalyst, including complex compounds that may be formed in situ by reaction between the catalyst and the hydrocarbons undergoing. treatment, so thatthe catalyst may be used more efiectively. .Aluminumchlochloride :containedin a complex material which is formed as anincident in the carryingout f theprinoipal conversion reaction. i

The invention has particular application to the isomerization of a saturated hydrocarbon such as normal butane. In accordance with theinven- 4.5

tiona stream of normal butane in vapor phase and heated to an elevated temperature is continuously introduced to thelowerportionof a packed reaction tower. Another stream of normal butane in liquidiphase and containingthe plex liq id which has a relatively low concentrametallic halide catalyst dissolved therein is "continuously introduced to thelupper portion of the tower. The stream of vaporizedcbutane rises throughthe packing within the tower countercurrently tothe downwardlyflflowing stream of .55

cracking occurs and consequently the efiuenthydrocarbon stream discharged iromthe top oi the l tower is substantially free fromgor contains a very small amount OfhYQIOQaIbO S or lower molecular weight than normal butane. i .y l

The efiiuent hydrocarbon stream is subsequent-.- ly subjected to fractionation if desiredior the purpose of eifecting. separation between normal butane and isobutane so that the normalbutane,

maybe recycledto thereaction. i

The eflluent hydrocarbonstream willcontain a substantial amount of hydrogen .chloride promoter and provision can be made for recovering the promoter and recycling it to the reaction. Likewise under certainiconditions of operation the .effluent hydrocarbons may .contain a small 'amountoi metallic halide and Provision may be made for efieoting removal of metallic halidefrom the hydrocarbons prior to the fractionating step. Suchremoval may be .efiected by .themical treatment or by passing the efiiuenthydrocarbon stream through a separateivessel packed Witha solid adsorptive material capable of effecting re moval of metallichalideby adsorption.

According to a modification of thepresent invention the efiluentjhydrocarbon stream of isom ate containing metallic halidemay be subjected tc-contact with metallic halide-hydrocarboncomtion of metallic halide, as, for example. the come plexliquid: discharged from the reaction tower.

and promoter from the isomate stream...

This complex is thus, usedto sorubtmetallic hal ide i temperature level.

As a result of such scrubbing the complex becomes enriched in metallic halide and promoter. Consequently, it may be desirable to recover from the enriched complex the metallic halide and promoter which has been scrubbed from the isomate stream. This can be accomplished by passing the enriched complex liquid material to a stripping zone wherein it is subjected to contact with a stream of feed hydrocarbons under conditions of temperature and pressure adapted to effect removal of the metallic halide and promoter at least to a substantial extent from the complex liquid. The resulting feed hydrocarbon stream containing metallic halide and promoter stripped from the complex is passed advantageously to the reaction tower as will be described in more detail upon reference to the drawing. I

In order to describe the invention more fully reference will now be made to the accompanying drawing comprising a diagram of flow illustrating one mode of practicing the invention.

As indicated in the drawing a stream of normal butane is drawn from a source not shown through apipe .l leading to an exchanger 2 wherein the temperature is brought to the desired level. From the exchanger 2 the butane stream passes through a pipe 3 to a vessel 4 containing solid aluminum chloride. During passage through the vessel a small amount of aluminum chloride is dissolved in the liquid butane stream. The amount dissolved depends upon thetemperature maintained which may be in the range 140 to 180 F. and also upon theam'ount of butane passing through the vessel 4. Usually the volume of butane passing through the vessel 4 does not exceed about /3 of thetotal volume of butane charged to the system and generally amounts to about /6 of the total.

, A bypass 30. maybe provided through which a such as Raschig rings, quartz, etc. The packing may extend to a depth ranging from'about 10 to '70 feet or more. Advantageously the interlor'of the tower may be provided with baifies, as indicated, to prevent the complex from running all the way down the interior wall of the tower.

Another portion of butane feed is diverted not shown through a pipe 14 which may communicate with the previously mentioned pipe l3.

Thus the butane vapors rise through the packing material in the reaction tower I and in doing so flow countercurrently to liquid hydrocarbons and catalyst descending from the upper portion of the tower. 1

The isomerization of normal butan to isobutane thus occurs during passage of the hydrocarbons and catalyst through the packing material. The treated hydrocarbons comprising isobutane are continuously drawn off from the top of the tower 1 through a pipe 20 which may lead to other apparatus wherein the isomate is subjected to treatment so as to effect recovery of entrained promoter and'any entrained catalyst as well as to efiect s'uch fractionation as may be desired.

The liquid accumulating in the bottom of the reaction tower 1 consist essentially of aluminum chloride-hydrocarbon complex and may have associated with it a small amount of hydrocarbons including tarry material. v 1

In descending toward the bottom of the reaction tower the complex has been broughtiinto intimate contact with fresh butane feed entering from the pipe I3. The rising butane stream tends to denude the complex of free aluminum chloride, the aluminum chloride so removed being used to efiect isomerization within the reaction tower; some of it entering into complex formationpso that it is ultimately consumed.

Consequently, the complex liquid as drawn .off from the bottom of the reaction tower I through the pipe 22 has a relatively low concentration of aluminum chloride. This complex can bedischarged from the system and disposed of-in any suitable manner including decomposition.

On the other hand this denuded complex material may be used as a scrubbing medium to scrub the isomate stream being discharged through the pipe 20 so as to effect removalfrom from the pipe I through a pipe I0 and a branch pipe I I leading to a heater l2 wherein the butane is heated to atemperature in the range 200 to 250 F. The heating temperature will depend upon the amount of heat required to maintain the reaction tower at the predetermined reaction Advantageously the heated butane enters the bottom of the reaction tower in vapor phase and superheated to a sufiiciently high temperature to supply the heat of reaction, and in-addition, the heat necessary for vaporizing the butane entering'the upper portion of the reaction tower through the pipe 5.

The heated vaporized butane thus passes from the heater l2 through a pipe l3 to th lower portion of the reaction tower I, advantageously at a point just below the packing. I 1 l Hydrogen chloride is introduced from a source the isomate of the small amount of aluminum chloride that may be contained therein as well as to effect removal of hydrogen chlorideat least in part. 7

Therefore, as indicated in the drawing all or a ber 25. I

Advantageously the isomate stream entering the scrubber 25 is first cooled during passage through a cooler 2'! to a temperature ranging from about '70 to F. The extent of coolin will depend upon the temperature conditions de-. sired to maintain in the scrubber 25 so as to "accomplish effective stripping of entrained alumi-". num chloride and promoterfrom the isomate.

The stripped isomate is continuously discharged from the top of the scrubber 25 through a pipe 28 which may lead to suitable fractionating equipment or to other apparatus depending upon the nature of the treatment desired. :1 I The enriched complex is drawn off from the bottom of the scrubber 25 through a pipe 29' and may be discharged from the system, or on the other hand conducted all or in part through a pipe 30 to a stripper 3|. The stripper 3| may be similar to the scrubber 25 and is utilized to effect recovery of aluminum chloride and promoter from the enriched com,

plexl The stripping agent advantageously com prises a portionofpthe butane teedwhich may be conducted from the previously mentioned pipe through a pipe 32 and heat exchanger 33 to the lower portion of the stripper 3|. A The butane advantageously inliquid phase rises through the stripper countercurrently to the enriched complex and thus efiects removal of aluminum chloride and promoter. Temperature conditions are maintained within the stripper 3! suitable to eflect solution of the aluminum chloride and ziromoterinv the stream of butane These temperatines may range from about 130 to 160 F; The ldenuded complex isdischarged from the bottom orthe stripper- 3! through a pipe 34.,

Thrbutane-stream containing aluminum chloride and promoter is conductor from the top of into thewreaction tower I at intermediate points,

thereof; a

'I'he' scrubber 25vand thestripper 3| maybe operated so that a substantial body of complex liquid is maintained therein vthrcugh whichthe hydrocarbons are caused to rise by dilference in specific gravity and iniwhichcase these vessels may contain no packing material.

Whilereterence has been made to maintaining thostripperltthroughrapipezti whichadvanat least the major portion oi. the hydrocarbon in r the reaction tower I in the vapor phase it is contemplated that the conversion reaction may be carried out with the feed hydrocarbon entirely in the liquidrph'ase: For example, the aluminum hydrocarbon undergoing conversion, the hydrocarbons thus rising through the catalyst solution by difference in density. a

Other metallic halides including aluminum bromide may be employed. Likewise the promoter may comprise other hydrogen halides besides the reaction in small and controlled amount for the purpose of inhibiting cracking or other side reactions so that isomerization constitutes the principal reaction. The reaction is carried out at temperatures ranging from about 150 to not in excess of about 300 to 350 F., depending upon the character of the feed hydrocarbon and the extent of conversion desired.

Obviously many modifications and variations of the invention, as hereinbefore set forth, may be made Without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

I claim: v

1. In a continuous process for isomerizing hychloridecatalyst may be added as a solution in a liquid of greaterspecific gravity than the feed isomerized hydrocarbon stream to produce enriched complex, dischargin the isomerized hydrocarbons by the action of a metallic halide isomerization catalyst in the presence of hydrogen other in the presence of hydrogen halide, maintaining said'j streams during said contact at a temperature such that isomerization of hydrocarbons constitutes the principal reaction, dischargmg a hydrocarbon stream comprising isomerized hydrocarbons and some metallic halide from the upper portionoflsaid tower,dischargingjliquid complex relatively lean in metallic halide from the lower portion of said tower, separatelysub-1 jecting said stream of isomerized hydrocarbon to contact with discharged complexliquidunder conditions such that the complex efiects: removal of metallic halide contained in the isomerizedhy drocarbon stream to produce enrichedcomplex and discharging jthe isomerized hydrocarbon stream from iurther contact with the complex liquid.

2. In a continuous process for? isomerizing hydrocarbons by the action ,o'fjfa metallic halide isomerization catalyst in the presenceof hydrogen halide under conditions such that some metallic halide-hydrocarbon complex i formed, thesteps comprising introducing a stream ofieed hydrocarbon ,at a, predetermined temperature to the lower portion'of a reaction towenintroducing a stream 'oi'liquid containing. metallic halide dissolved therein to theupper portion of said tower, passing said streams countercurrently through the tower while in intimate contact with each other in the presence of hydrogen halide, maintaining said streams during said contact at a temperature such that, isomerization of hydrocarbons'constitutes the principalreaction, discharging a hydrocarbon stream comprising isomerized hydrocarbons and som metallic halide from the upper portion of said tower, discharging liquid complex relatively lean in metallic halide from the lower portion of said tower, separately subjecting said stream of isomerized hydrocarbons to contact with discharged complex liquid under conditions such that the complex effects removal of metallic halide contained in the drocarbon stream from further contact with the complex liquid, subjecting the enriched complex liquid to contact with a portion of the feed hydrocarbon under conditions such that the feed hydrocarbon strips metallic halide from the complex, and passing the feedhydrocarbons containing metallic halide stripped from the complex to the reaction tower.

3. In a continuous process for isomerizing hydrocarbons by the action of a metallic halide isomerization catalyst in the presence of hydrogen halide in a reaction tower packed with solid inert contact material and under conditions such that some metallic halide-hydrocarbon complex is formed in situ by reaction between feed hydrocarbons and metallic halide, the steps comprising forming a stream comprising the major proportion of the hydrocarbon feed and a stream in r liquid phase comprising the minor proportion of the hydrocarbon feed, dissolving metallic halide in the liquid stream of minor proportion, introducing the stream containing dissolved metallic halide to the tower'above the mass "ofvcontact material, introducing the stream of majorpro portion to the lowerportion-of the tower; heat-v ing said last-mentioned'stream, prior tointroe duction, to a predetermined temperature sufiicient to maintain the reaction tower under'isomerizing conditions of temperature; causing the :heated stream to rise through the contact mass in'the presence of hydrogen halide countercurrently-to catalyst descending in liquid phase, said catalyst W discharging the isomerized hydrocarbons from further'contact with'the complex liquid. I

4. The process according to claim 3 in which the heated stream of feed hydrocarbon is introduced to the reaction tower in vapor phase.

5. The process according to claim 3 in which the isomerization catalyst is aluminum halide" 6. In a continuous process for isomerizing normal butane by the action of an aluminum halide isomerization catalyst in the presence of hydrogen halidein a reaction tower packed with solid inert contact material and under conditions such that some aluminum halide-hydrocarbon complex is formed in situ by reaction between normal butane and aluminum halide, the steps comprising forming a stream comprising'the major proportion of the normal butane feed and a stream in liquid phase comprising the minor proportion of the normal butane feed, dissolving aluminum halide in the liquid stream of minor proportion, introducing the stream containing dissolved'aluminum halide to the tower above the mass of contact material, introducing the stream of major proportion to the lower portion of the tower, heating said last-mentioned stream, prior to-'introduction,'to' a predetermined temperature; sufficient to maintain the reaction tower under isomerizing conditions of temperature, causin the heated stream tor'ise through the contact mass in the presence of'hydrogen halide counter'currently to catalyst descending in liquidphase, said catalyst comprising aluminum halide and -alu-';

minum halide-hydrocarbon complex iormed in situ, effecting substantial isomerization of normal butane during flow through the contact mass, dis charging isomerized normal butane and some aluminum halide from the upper portion of said tower, discharging from the bottom portion'ofthe tower liquid complex having a relatively low con: centration of aluminum halide, separately subjecting said discharged isomerized normal-butane to contact with said discharged liquid complex under conditions such that the complex effects removal of aluminum halide contained in the iso-v merized butane to produce enriched complex, and then discharging the isomerized butane from further contact with the complex liquid.

'7. The process according to claim 6 in ,whic the reaction is efiected at a temperature in-the range ISO-240 F. WYNKOOP KIERS'IED, JR. 

